Alloying noble metals with non-noble metals enables high activity while reducing the cost of electrocatalysts in fuel cells. However, under fuel cell operating conditions, state-of-the-art oxygen reduction reaction alloy catalysts either feature high atomic percentages of noble metals (>70%) with limited durability or show poor durability when lower percentages of noble metals (<50%) are used. Here, we demonstrate a highly-durable alloy catalyst derived by alloying PtPd (<50%) with 3d-transition metals (Cu, Ni or Co) in ternary compositions. The origin of the high durability is probed by in-situ/operando high-energy synchrotron X-ray diffraction coupled with pair distribution function analysis of atomic phase structures and strains, revealing an important role of realloying in the compressively-strained single-phase alloy state despite the occurrence of dealloying. The implication of the finding, a striking departure from previous perceptions of phase-segregated noble metal skin or complete dealloying of non-noble metals, is the fulfilling of the promise of alloy catalysts for mass commercialization of fuel cells.

The ability to control the surface composition and morphology of alloy catalysts is critical for achieving high activity and durability of catalysts for oxygen reduction reaction (ORR) and fuel cells. This report describes an efficient surfactant-free synthesis route for producing a twisty nanowire (TNW) shaped platinum−iron (PtFe) alloy catalyst (denoted as PtFe TNWs) with controllable bimetallic compositions. PtFe TNWs with an optimal initial composition of ∼24% Pt are shown to exhibit the highest mass activity (3.4 A/mg Pt , ∼20 times higher than that of commercial Pt catalyst) and the highest durability (<2% loss of activity after 40 000 cycles and <30% loss after 120 000 cycles) among all PtFe-based nanocatalysts under ORR or fuel cell operating conditions reported so far. Using ex situ and in situ synchrotron X-ray diffraction coupled with atomic pair distribution function (PDF) analysis and 3D modeling, the PtFe TNWs are shown to exhibit mixed face-centered cubic (fcc)−body-centered cubic (bcc) alloy structure and a significant lattice strain. A striking finding is that the activity strongly depends on the composition of the as-synthesized catalysts and this dependence remains unchanged despite the evolution of the composition of the different catalysts and their lattice constants under ORR or fuel cell operating conditions. Notably, dealloying under fuel cell operating condition starts at phase-segregated domain sites leading to a final fcc alloy structure with subtle differences in surface morphology. Due to a subsequent realloying and the morphology of TNWs, the surface lattice strain observed with the as-synthesized catalysts is largely preserved. This strain and the particular facets exhibited by the TNWs are believed to be responsible for the observed activity and durability enhancements. These findings provide new insights into the correlation between the structure, activity, and durability of nanoalloy catalysts and are expected to energize the ongoing effort to develop highly active and durable low-Pt-content nanowire catalysts by controlling their alloy structure and morphology.

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A new series of novel dicationic symmetrical and asymmetrical ionic liquids (ILs) consisting of tributylalkyl phosphonium and alkylimidazolium were synthesized. Their tribological properties in the form of spin-coated ultra-thin films sliding against AISI-52100 steel ball were studied in a ball-on-plate configuration on a Universal Micro-tribometer-2MT tester, using perfluoropolyether (PFPE) and normal ILs as comparisons. The best result is obtained for asymmetrical 1-(1-tributylphosphine-yl-hexyl)-3-methylimidazolium dihexafluorophosphate, which has very high decomposition temperature-about 450°C and good tribological properties.

This report describes new findings of an investigation of a bifunctional nanocomposite probe for the detection of cancer biomarkers, demonstrating the viability of magnetic focusing and SERS detection in a microfluidic platform. The nanocomposite probe consists of a magnetic nickel-iron core and a gold shell. Upon bioconjugation, the nanoprobes are magnetically focused on a specific spot in a microfluidic channel, enabling an enrichment of "hot spots" for surface enhanced Raman scattering detection of the targeted carcinoembryonic antigen. The detection sensitivity, with a limit of detection of ∼0.1 pM, is shown to scale with the magnetic focusing time and the nanoparticle size. The latter is also shown to exhibit an excellent agreement between the experimental data and the theoretical simulation. Implications of the findings to the development of rapid and sensitive microfluidic detection of cancer biomarkers are also discussed.

LiNi0.6Mn0.2Co0.2O2 (NMC622) is one of the most promising Li-ion battery cathodes as it delivers high capacity at high potentials. However, high potentials also lead to decreases in capacity retention where the disintegration of the secondary particles has been implicated as a major driving force of this capacity fade. This has been attributed to anisotropic lattice changes and increased microstrain during cycling. To probe how these factors affect capacity fade, Li/NMC622 batteries were cycled from 3 to 4.3 or 4.7 V and probed with operando X-ray diffraction (XRD) over the 1st, 2nd, and 101st cycles. Further characterization with scanning electron microscopy and inductively coupled plasma-optical emission spectroscopy was also performed. The use of operando XRD over many cycles allowed for the collection of detailed structural information in real time over a time frame in which fading can be observed. During the first two cycles, the cells charged to 4.7 V exhibit increased anisotropic lattice changes as compared to the cells charged to 4.3 V. Upon the 101st cycle, when significant fade has been observed, the cells charged to 4.3 and 4.7 V show identical lattice changes to one another, while the 4.7 V charge limit induces more microstrain. This shows that elevated microstrain at high charge limits is a major driver for particle disintegration in NMC622 cathodes. This study provides important insights into the mechanisms of particle disintegration and capacity fade in NMC/Li-ion batteries, which will enable the design of NMC electrodes that deliver both higher capacities and exhibit better capacity retention.

Two nanostructured proton-containing δ-MnO2 (H-δ-MnO2) materials were synthesized through proton exchange for K-containing δ-MnO2 (K-δ-MnO2) nanosheets and nanoparticles prepared by the hydrothermal homogeneous precipitation method and solid-state reaction.

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